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Article(id=1322912294639903277, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1322912162913596032, articleNumber=null, orderNo=null, doi=10.13193/j.issn.1673-7717.2025.01.024, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=null, receivedDateStr=null, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1793336469563, onlineDateStr=2026-10-30, pubDate=1736438400000, pubDateStr=2025-01-10, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793336469563, onlineIssueDateStr=2026-10-30, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793336469563, creator=13701087609, updateTime=1793336469563, updator=13701087609, issue=Issue{id=1322912162913596032, tenantId=1146029695717560320, journalId=1255847919539208197, year='2025', volume='43', issue='1', pageStart='1', pageEnd='258', issueExtLink='null', onlineDate='null', pubDate='1736438400000', pubDateStr='2025-01-10', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1793336438157, creator='13701087609', updateTime=1793340633627, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1322929760048906989, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1322912162913596032, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1322929760048906990, tenantId=1146029695717560320, journalId=1255847919539208197, issueId=1322912162913596032, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=134, endPage=141, ext={EN=ArticleExt(id=1322912294858007086, articleId=1322912294639903277, tenantId=1146029695717560320, journalId=1255847919539208197, language=EN, title=Analysis of Odor Substance Difference from Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）by Electronic Nose and GC-IMS, columnId=1256183361521967297, journalTitle=Chinese Archives of Traditional Chinese Medicine, columnName=Target on National Project, runingTitle=null, highlight=null, articleAbstract=
Objective

To study the difference in odor substances between Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）.

Methods

Electronic nose technology and gas chromatography-ionmobility spectroscopy（GC-IMS）were used to detectvolatile substances in the Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The NIST and IMS databases were used to qualitatively and quantitatively analyze volatile substances. Plug-ins for the instrumentwas used to perform the dynamic principal component analysis of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The SIMCA-P 14.0 software was used to perform orthogonal partial least squares-discriminant analysis of volatile substances. The microbiotic platform was used to perform cluster heatmap analysis of volatile substances. The fingerprints and the characteristic component of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）sampleswere compared and analyzed. The volatile substances of students't-test with P<0.05 and orthogonal partial least squares-discriminantanalysis with VIP>1 were selected asmarkers of odor differences.

Results

There were significant differences in the volatile components of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium. Four characteristic substances were identified in Nanchaihu（B. Scorzonerifolium），namely decanal-M，linalool oxide，2，3-diethyl-5-methylpyrazine and 3-methyl-2-butenal-D. Two characteristic substances were identified in Beichaihu（Bupleurum Chinense），namely 3-methylbutanol-D and 2-methylpropanoic acid. A total of 24 markers of odor differences were screened，which could be used as the basis for distinguishing between Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）.

Conclusion

The GC-IMS or electronic nose technology can quickly identify Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The gas of rancid oil of Nanchaihu（B. Scorzonerifolium）may be related to its characteristic substance 3-methyl-2-butenal-D and markers of odor differences such as decanal，（E）-2-hexenal，octanal，heptanal，hexanal，acrolein，isobutanal，et al.

, authors=Shili WANG1, Juanjuan ZHU2, 3, Chang LYU2, 3, Yanpeng DAI2, 3, Jun ZHANG2, 3, Dianhua SHI2, 3, authorsList=Shili WANG, Juanjuan ZHU, Chang LYU, Yanpeng DAI, Jun ZHANG, Dianhua SHI, authorCompany=null, correspAuthors=Jun ZHANG, Dianhua SHI, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1322912298397999683, articleId=1322912294639903277, tenantId=1146029695717560320, journalId=1255847919539208197, language=CN, title=基于电子鼻和气相离子迁移谱技术分析南北柴胡气味物质差异, columnId=1256183362172142382, journalTitle=中华中医药学刊, columnName=国家项目点击, runingTitle=null, highlight=null, articleAbstract=
目的

研究南北柴胡气味物质差异。

方法

应用电子鼻技术和气相色谱-离子迁移谱联用（GC-IMS）技术检测南北柴胡挥发性物质差异，采用NIST、IMS数据库对挥发性物质进行定性和定量分析；使用仪器配套的插件对南北柴胡样品进行动态主成分分析（Dynamic PCA），利用SIMCA-P 14.0软件对其进行正交偏最小二乘法-判别分析（OPLS-DA），以微生信平台对其进行聚类热图分析；对比南北柴胡指纹图谱，分析南北柴胡特征物质，筛选Student's t-test P<0.05且正交偏最小二乘法-判别分析模型中变量投影重要性（VIP）>1的挥发性物质为气味差异标志物。

结果

南北柴胡挥发性成分具有显著差异，南柴胡辨识出4个特征物质，分别是癸醛（单体）、氧化芳樟醇、2，3-二乙基-5-甲基吡嗪、异戊烯醛（二聚体）；北柴胡辨识出2个特征物质，分别是3-甲基丁醇（二聚体）、2-甲基丙酸。共筛选出24个气味差异标志物，这些成分可以作为区分南北柴胡的依据。

结论

应用GC-IMS或电子鼻气味辨识技术能够快速鉴别南北柴胡，南柴胡败油气可能与其特征物质异戊烯醛（二聚体）及气味差异标志物癸醛、反-4-己烯醛、正辛醛、庚醛、正己醛、丙烯醛、异丁醛等醛类物质有关。

, authors=王世丽1, 朱娟娟2, 3, 吕畅2, 3, 戴衍朋2, 3, 张军2, 3, 石典花2, 3, authorsList=王世丽, 朱娟娟, 吕畅, 戴衍朋, 张军, 石典花, authorCompany=null, correspAuthors=张军, 石典花, authorNote=

王世丽（1999-），女，山东聊城人，硕士，研究方向：中药炮制。

, correspAuthorsNote=
张军（1979-），男，山东济南人，研究员，学士，研究方向：中药炮制。E-mail：。
石典花（1981-），女，山东济南人，研究员，硕士研究生导师，博士，研究方向：中药炮制。E-mail：。
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王世丽（1999-），女，山东聊城人，硕士，研究方向：中药炮制。

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王世丽（1999-），女，山东聊城人，硕士，研究方向：中药炮制。

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注：A.南柴胡2；B.北柴胡2；C.南柴胡2雷达图（117 s）；D.北柴胡2雷达图（117 s）。

, figureFileSmall=UVa1eyLqNqK5Pe9mFQQ2fg==, figureFileBig=BKrdB+rJaOaLGv6BXhj4Iw==, tableContent=null), ArticleFig(id=1322912487712109014, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=EN, label=null, caption=null, figureFileSmall=dllEMpVToaDDVF4Hx+Rc7g==, figureFileBig=H7IOnerEIppanFKrxvJPXw==, tableContent=null), ArticleFig(id=1322912487800189399, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=图2, caption=南北柴胡电子鼻检测数据的PCA

注：黑色数字表示二者具有显著性差异。

, figureFileSmall=dllEMpVToaDDVF4Hx+Rc7g==, figureFileBig=H7IOnerEIppanFKrxvJPXw==, tableContent=null), ArticleFig(id=1322912487879881176, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=EN, label=null, caption=null, figureFileSmall=6nCZPG8aKRwaLsvmqXK92g==, figureFileBig=z5l17VEZWEr3T5uSMZqvTA==, tableContent=null), ArticleFig(id=1322912487967961561, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=图3, caption=南北柴胡电子鼻检测数据的LDA, figureFileSmall=6nCZPG8aKRwaLsvmqXK92g==, figureFileBig=z5l17VEZWEr3T5uSMZqvTA==, tableContent=null), ArticleFig(id=1322912488060236250, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=EN, label=null, caption=null, figureFileSmall=G4EPLgsL8Fj9sBAkpZslJg==, figureFileBig=rV8nadLRQmLbADCmQEJwiA==, tableContent=null), ArticleFig(id=1322912488135733723, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=图4, caption=南北柴胡电子鼻特征气味差异分析

注：A.南北柴胡电子鼻检测数据的OPLS-DA分析；B.南北柴胡电子鼻检测数据OPLS-DA分析模型的置换检验图；C.南北柴胡电子鼻检测数据OPLS-DA分析的VIP值；D.南北柴胡电子鼻检测数据的Loading图。

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样品名称基原来源
BC1北柴胡山东百味堂中药饮片有限公司
BC2北柴胡山东百味堂中药饮片有限公司
BC3北柴胡山东百味堂中药饮片有限公司
NC1南柴胡林甸县大山中草药种植农民合作社
NC2南柴胡林甸县大山中草药种植农民合作社
NC3南柴胡亳州药材市场
), ArticleFig(id=1322912490929140201, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=表1, caption=

样品信息

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称基原来源
BC1北柴胡山东百味堂中药饮片有限公司
BC2北柴胡山东百味堂中药饮片有限公司
BC3北柴胡山东百味堂中药饮片有限公司
NC1南柴胡林甸县大山中草药种植农民合作社
NC2南柴胡林甸县大山中草药种植农民合作社
NC3南柴胡亳州药材市场
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阵列序号传感器名称性能描述
1W1C芳香成分，苯类
2W5S灵敏度大，对氮氧化合物很灵敏
3W3C氨水，对芳香成分灵敏
4W6S主要对氢气有选择性
5W5C烷烃芳香成分
6W1S对甲烷等短链烷烃灵敏
7W1W对无机硫化物灵敏
8W2S对醇醚醛酮类灵敏
9W2W芳香成分，对有机硫化物灵敏
10W3S对烷烃灵敏，长链烷烃类
), ArticleFig(id=1322912491101106667, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=表2, caption=

传感器名称及性能描述

, figureFileSmall=null, figureFileBig=null, tableContent=
阵列序号传感器名称性能描述
1W1C芳香成分，苯类
2W5S灵敏度大，对氮氧化合物很灵敏
3W3C氨水，对芳香成分灵敏
4W6S主要对氢气有选择性
5W5C烷烃芳香成分
6W1S对甲烷等短链烷烃灵敏
7W1W对无机硫化物灵敏
8W2S对醇醚醛酮类灵敏
9W2W芳香成分，对有机硫化物灵敏
10W3S对烷烃灵敏，长链烷烃类
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软件及插件名称应用
VOCal用于查看分析谱图和数据的定性定量，应用软件内置的NIST数据库和IMS数据库可对物质进行定性分析，图中每一个点代表一种挥发性有机物，对其建立标准曲线后可进行定量分析
Reporter插件直接对比样品之间的谱图差异（三维谱图、二维俯视图和差异谱图）
Gallery Plot插件指纹图谱对比，直观且定量地比较不同样品之间的挥发性有机物差异
Dynamic PCA插件动态主成分分析，用于将样品聚类分析，以及快速确定未知样品的种类
), ArticleFig(id=1322912491369542125, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=表3, caption=

软件及插件的应用信息

, figureFileSmall=null, figureFileBig=null, tableContent=
软件及插件名称应用
VOCal用于查看分析谱图和数据的定性定量，应用软件内置的NIST数据库和IMS数据库可对物质进行定性分析，图中每一个点代表一种挥发性有机物，对其建立标准曲线后可进行定量分析
Reporter插件直接对比样品之间的谱图差异（三维谱图、二维俯视图和差异谱图）
Gallery Plot插件指纹图谱对比，直观且定量地比较不同样品之间的挥发性有机物差异
Dynamic PCA插件动态主成分分析，用于将样品聚类分析，以及快速确定未知样品的种类
), ArticleFig(id=1322912491466011118, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
序号tR/s化合物名称分子式相对分子质量保留指数相对迁移时间备注
11 505.371丙酸（propanoic acid）C3H6O274.11 590.41.114 2
21 490.2102-甲基丙酸（2-methylpropanoic acid）C4H8O288.11 587.11.1498
31 506.749芳樟醇（linalool）C10H18O154.31 590.71.223 1单体
41 390.975顺-4-癸烯醛［（Z）-4-decenal］C10H18O154.31 564.41.338 3
51 209.044癸醛（decanal）C10H20O156.31 518.31.544 6单体
61 207.666癸醛（decanal）C10H20O156.31 517.92.056 6二聚体
71 265.553苯甲醛（benzaldehyde）C7H6O106.11 533.31.156 0
81 111.187冰醋酸（acetic acid）C2H4O260.11 490.51.054 5单体
91 111.187冰醋酸（acetic acid）C2H4O260.11 490.51.156 0二聚体
10945.953反-2-辛烯醛［（E）-2-octenal］C8H14O126.21 437.61.335 1单体
11947.352反-2-辛烯醛［（E）-2-octenal］C8H14O126.21 438.11.824 3二聚体
12929.859氧化芳樟醇（linalool oxide）C10H18O2170.31 431.91.254 0
13888.846二甲基三硫醚（dimethyltrisulfide）C2H6S3126.31 417.11.295 8
141 131.5952，3-二乙基-5-甲基吡嗪（2，3-diethyl-5-methylpyrazine）C9H14N2150.21 496.51.260 1
15887.1883-辛醇（3-octanol）C8H18O130.21 416.51.778 6
16855.720壬醛（nonanal）C9H18O142.21 404.61.478 6单体
17851.524壬醛（nonanal）C9H18O142.21 403.01.945 9二聚体
18770.754正己醇（1-hexanol）C6H14O102.21 370.21.327 9单体
19769.705正己醇（1-hexanol）C6H14O102.21 369.71.638 9二聚体
20722.174甜瓜醛（2，6-dimethyl-5-heptenal）C9H16O140.21 348.81.178 0
21710.588庚酸乙酯（ethyl heptanoate）C9H18O2158.21 343.41.411 8单体
22710.588庚酸乙酯（ethyl heptanoate）C9H18O2158.21 343.41.915 9二聚体
23686.771反式-2-已烯-1-醇［（E）-2-heptenal］C7H12O112.21 332.21.257 0单体
24684.840反式-2-已烯-1-醇［（E）-2-heptenal］C7H12O112.21 331.31.671 4二聚体
25655.8742-乙基吡嗪（ethylpyrazine）C6H8N2108.11 317.11.140 6
26646.862萜品油烯（terpinolene）C10H16136.21 312.51.204 7
27624.332正辛醛（octanal）C8H16O128.21 300.91.404 4单体
28622.401正辛醛（octanal）C8H16O128.21 299.91.828 4二聚体
29612.1022-辛酮（octan-2-one）C8H16O128.21 294.31.335 0单体
30614.0332-辛酮（2-octanone）C8H16O128.21 295.41.760 0二聚体
31595.366乙酸己酯（hexyl acetate）C8H16O2144.21 284.11.389 4单体
32595.366乙酸己酯（hexyl acetate）C8H16O2144.21 284.11.899 9二聚体
33563.825正戊醇（1-pentanol）C5H12O88.11 263.91.255 9单体
34562.537正戊醇（1-pentanol）C5H12O88.11 263.11.511 2二聚体
35529.7092-戊基呋喃（2-pentylfuran）C9H14O138.21 240.91.253 8
36533.571正己酸乙酯（ethyl hexanoate）C8H16O2144.21 243.61.341 4单体
37532.927正己酸乙酯（ethyl hexanoate）C8H16O2144.21 243.11.801 7二聚体
38513.616反-4-己烯醛［（E）-2-hexenal］C6H10O98.11 229.51.182 2单体
39513.616反-4-己烯醛［（E）-2-hexenal］C6H10O98.11 229.51.521 9二聚体
40490.504异戊烯醛（3-methyl-2-butenal）C5H8O84.11 212.51.092 6单体
41490.828异戊烯醛（3-Methyl-2-butenal）C5H8O84.11 212.71.359 5二聚体
42470.699庚醛（heptanal）C7H14O114.21 197.31.329 7单体
43471.023庚醛（heptanal）C7H14O114.21 197.51.693 8二聚体
44465.5042-庚酮（heptan-2-one）C7H14O114.21 193.21.632 3
45467.777柠檬烯（limonene）C10H16136.21 195.01.662 0
46455.764乙酸戊酯（pentyl acetate）C7H14O2130.21 184.91.312 9单体
47455.439乙酸戊酯（pentyl acetate）C7H14O2130.21 184.61.766 2二聚体
48442.128α-松油烯（alpha-terpinene）C10H16136.21 172.91.203 7
49422.323正丁醇（butan-1-ol）C4H10O74.11 154.81.181 9单体
50423.622正丁醇（butan-1-ol）C4H10O74.11 156.01.379 3二聚体
51371.026正己醛（hexanal）C6H12O100.21 103.71.564 8
52413.557δ-3-蒈烯（delta-3-carene）C10H16136.21 146.51.680 9
53412.2594-甲基-2-戊醇（4-methyl-2-pentanol）C6H14O102.21 145.31.545 0
54396.674β-蒎烯（beta-pinene）C10H16136.21 130.11.217 6单体
55364.8572-己酮（hexan-2-one）C6H12O100.21 097.01.501 3
56391.480β-蒎烯（beta-pinene）C10H16136.21 124.91.642 2二聚体
57358.039乙酸丁酯（butyl acetate）C6H12O2116.21 088.31.238 5单体
58357.714乙酸丁酯（butyl acetate）C6H12O2116.21 087.91.618 4二聚体
59349.5987，7-二甲基-3-亚甲基双环［2.2.1］庚烷C10H16136.21 077.31.215 6
60337.909莰烯（camphene）C10H16136.21 061.51.200 8
61331.301丁酸乙酯（ethyl butanoate）C6H12O2116.21 052.41.212 1单体
62330.310丁酸乙酯（ethyl butanoate）C6H12O2116.21 051.01.560 9二聚体
63320.896α-蒎烯（alpha-pinene）C10H16136.21 037.61.217 5单体
64319.905α-蒎烯（alpha-pinene）C10H16136.21 036.21.664 3二聚体
65319.740α-蒎烯（alpha-pinene）C10H16136.21 035.91.732 7三聚体
66313.9604-甲基-2-戊酮（4-methyl-2-pentanone）C6H12O100.21 027.51.178 8
67298.105正戊醛（pentanal）C5H10O86.11 003.51.426 1
68293.8112-戊酮（pentan-2-one）C5H10O86.1996.81.369 4
69269.369乙醇（ethanol）C2H6O46.1943.71.138 4
70281.425丙酸乙酯（ethyl propanoate）C5H10O2102.1970.61.453 0
71261.4412-甲基丁醛（2-methylbutanal）C5H10O86.1925.41.400 0
72256.982甲乙酮（butan-2-one）C4H8O72.1914.81.245 3
73250.211乙酸乙酯（ethyl acetate）C4H8O288.1898.41.338 0
74246.247丁醛（butanal）C4H8O72.1888.61.280 4
75238.155丙烯醛（acrolein）C3H4O56.1868.11.059 2
76232.209乙酸甲酯（methyl acetate）C3H6O274.1852.61.195 0
77222.630丙醛（propanal）C3H6O58.1826.71.141 4
78227.760异丁醛（isobutanal）C4H8O72.1840.71.113 1单体
79226.130异丁醛（isobutanal）C4H8O72.1836.31.282 9二聚体
80215.145甲酸乙酯（ethyl formate）C3H6O274.1805.71.087 1
81498.657异戊醇（3-methyl-1-butanol）C5H12O88.11 218.61.244 8单体
82497.915异戊醇（3-methylbutanol）C5H12O88.11 218.01.491 0二聚体
), ArticleFig(id=1322912491558285807, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=表4, caption=

南北柴胡中挥发性有机物成分辨识

, figureFileSmall=null, figureFileBig=null, tableContent=
序号tR/s化合物名称分子式相对分子质量保留指数相对迁移时间备注
11 505.371丙酸（propanoic acid）C3H6O274.11 590.41.114 2
21 490.2102-甲基丙酸（2-methylpropanoic acid）C4H8O288.11 587.11.1498
31 506.749芳樟醇（linalool）C10H18O154.31 590.71.223 1单体
41 390.975顺-4-癸烯醛［（Z）-4-decenal］C10H18O154.31 564.41.338 3
51 209.044癸醛（decanal）C10H20O156.31 518.31.544 6单体
61 207.666癸醛（decanal）C10H20O156.31 517.92.056 6二聚体
71 265.553苯甲醛（benzaldehyde）C7H6O106.11 533.31.156 0
81 111.187冰醋酸（acetic acid）C2H4O260.11 490.51.054 5单体
91 111.187冰醋酸（acetic acid）C2H4O260.11 490.51.156 0二聚体
10945.953反-2-辛烯醛［（E）-2-octenal］C8H14O126.21 437.61.335 1单体
11947.352反-2-辛烯醛［（E）-2-octenal］C8H14O126.21 438.11.824 3二聚体
12929.859氧化芳樟醇（linalool oxide）C10H18O2170.31 431.91.254 0
13888.846二甲基三硫醚（dimethyltrisulfide）C2H6S3126.31 417.11.295 8
141 131.5952，3-二乙基-5-甲基吡嗪（2，3-diethyl-5-methylpyrazine）C9H14N2150.21 496.51.260 1
15887.1883-辛醇（3-octanol）C8H18O130.21 416.51.778 6
16855.720壬醛（nonanal）C9H18O142.21 404.61.478 6单体
17851.524壬醛（nonanal）C9H18O142.21 403.01.945 9二聚体
18770.754正己醇（1-hexanol）C6H14O102.21 370.21.327 9单体
19769.705正己醇（1-hexanol）C6H14O102.21 369.71.638 9二聚体
20722.174甜瓜醛（2，6-dimethyl-5-heptenal）C9H16O140.21 348.81.178 0
21710.588庚酸乙酯（ethyl heptanoate）C9H18O2158.21 343.41.411 8单体
22710.588庚酸乙酯（ethyl heptanoate）C9H18O2158.21 343.41.915 9二聚体
23686.771反式-2-已烯-1-醇［（E）-2-heptenal］C7H12O112.21 332.21.257 0单体
24684.840反式-2-已烯-1-醇［（E）-2-heptenal］C7H12O112.21 331.31.671 4二聚体
25655.8742-乙基吡嗪（ethylpyrazine）C6H8N2108.11 317.11.140 6
26646.862萜品油烯（terpinolene）C10H16136.21 312.51.204 7
27624.332正辛醛（octanal）C8H16O128.21 300.91.404 4单体
28622.401正辛醛（octanal）C8H16O128.21 299.91.828 4二聚体
29612.1022-辛酮（octan-2-one）C8H16O128.21 294.31.335 0单体
30614.0332-辛酮（2-octanone）C8H16O128.21 295.41.760 0二聚体
31595.366乙酸己酯（hexyl acetate）C8H16O2144.21 284.11.389 4单体
32595.366乙酸己酯（hexyl acetate）C8H16O2144.21 284.11.899 9二聚体
33563.825正戊醇（1-pentanol）C5H12O88.11 263.91.255 9单体
34562.537正戊醇（1-pentanol）C5H12O88.11 263.11.511 2二聚体
35529.7092-戊基呋喃（2-pentylfuran）C9H14O138.21 240.91.253 8
36533.571正己酸乙酯（ethyl hexanoate）C8H16O2144.21 243.61.341 4单体
37532.927正己酸乙酯（ethyl hexanoate）C8H16O2144.21 243.11.801 7二聚体
38513.616反-4-己烯醛［（E）-2-hexenal］C6H10O98.11 229.51.182 2单体
39513.616反-4-己烯醛［（E）-2-hexenal］C6H10O98.11 229.51.521 9二聚体
40490.504异戊烯醛（3-methyl-2-butenal）C5H8O84.11 212.51.092 6单体
41490.828异戊烯醛（3-Methyl-2-butenal）C5H8O84.11 212.71.359 5二聚体
42470.699庚醛（heptanal）C7H14O114.21 197.31.329 7单体
43471.023庚醛（heptanal）C7H14O114.21 197.51.693 8二聚体
44465.5042-庚酮（heptan-2-one）C7H14O114.21 193.21.632 3
45467.777柠檬烯（limonene）C10H16136.21 195.01.662 0
46455.764乙酸戊酯（pentyl acetate）C7H14O2130.21 184.91.312 9单体
47455.439乙酸戊酯（pentyl acetate）C7H14O2130.21 184.61.766 2二聚体
48442.128α-松油烯（alpha-terpinene）C10H16136.21 172.91.203 7
49422.323正丁醇（butan-1-ol）C4H10O74.11 154.81.181 9单体
50423.622正丁醇（butan-1-ol）C4H10O74.11 156.01.379 3二聚体
51371.026正己醛（hexanal）C6H12O100.21 103.71.564 8
52413.557δ-3-蒈烯（delta-3-carene）C10H16136.21 146.51.680 9
53412.2594-甲基-2-戊醇（4-methyl-2-pentanol）C6H14O102.21 145.31.545 0
54396.674β-蒎烯（beta-pinene）C10H16136.21 130.11.217 6单体
55364.8572-己酮（hexan-2-one）C6H12O100.21 097.01.501 3
56391.480β-蒎烯（beta-pinene）C10H16136.21 124.91.642 2二聚体
57358.039乙酸丁酯（butyl acetate）C6H12O2116.21 088.31.238 5单体
58357.714乙酸丁酯（butyl acetate）C6H12O2116.21 087.91.618 4二聚体
59349.5987，7-二甲基-3-亚甲基双环［2.2.1］庚烷C10H16136.21 077.31.215 6
60337.909莰烯（camphene）C10H16136.21 061.51.200 8
61331.301丁酸乙酯（ethyl butanoate）C6H12O2116.21 052.41.212 1单体
62330.310丁酸乙酯（ethyl butanoate）C6H12O2116.21 051.01.560 9二聚体
63320.896α-蒎烯（alpha-pinene）C10H16136.21 037.61.217 5单体
64319.905α-蒎烯（alpha-pinene）C10H16136.21 036.21.664 3二聚体
65319.740α-蒎烯（alpha-pinene）C10H16136.21 035.91.732 7三聚体
66313.9604-甲基-2-戊酮（4-methyl-2-pentanone）C6H12O100.21 027.51.178 8
67298.105正戊醛（pentanal）C5H10O86.11 003.51.426 1
68293.8112-戊酮（pentan-2-one）C5H10O86.1996.81.369 4
69269.369乙醇（ethanol）C2H6O46.1943.71.138 4
70281.425丙酸乙酯（ethyl propanoate）C5H10O2102.1970.61.453 0
71261.4412-甲基丁醛（2-methylbutanal）C5H10O86.1925.41.400 0
72256.982甲乙酮（butan-2-one）C4H8O72.1914.81.245 3
73250.211乙酸乙酯（ethyl acetate）C4H8O288.1898.41.338 0
74246.247丁醛（butanal）C4H8O72.1888.61.280 4
75238.155丙烯醛（acrolein）C3H4O56.1868.11.059 2
76232.209乙酸甲酯（methyl acetate）C3H6O274.1852.61.195 0
77222.630丙醛（propanal）C3H6O58.1826.71.141 4
78227.760异丁醛（isobutanal）C4H8O72.1840.71.113 1单体
79226.130异丁醛（isobutanal）C4H8O72.1836.31.282 9二聚体
80215.145甲酸乙酯（ethyl formate）C3H6O274.1805.71.087 1
81498.657异戊醇（3-methyl-1-butanol）C5H12O88.11 218.61.244 8单体
82497.915异戊醇（3-methylbutanol）C5H12O88.11 218.01.491 0二聚体
), ArticleFig(id=1322912491637977584, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=EN, label=null, caption=null, figureFileSmall=null, figureFileBig=null, tableContent=
编号化合物峰强度VIPP值
北柴胡1北柴胡2北柴胡3北柴胡4北柴胡5北柴胡6
1芳樟醇（单体）202033576258<1-
2顺-4-癸烯醛201321605151<1-
3癸醛（单体）2921182702362451.1380.000
4癸醛（二聚体）131414474045<1-
5反-2-辛烯醛（单体）1267986297248259<1-
6反-2-辛烯醛（二聚体）151612394147<1-
7氧化芳樟醇231615152169164<1-
8二甲基三硫醚129102115277238253<1-
92，3-二乙基-5-甲基吡嗪3416162913153111.2780.000
103-辛醇171417544653<1-
11壬醛（单体）115126112223168186<1-
12壬醛（二聚体）151414252023<1-
13正己醇（二聚体）2632501364754794751.1980.023
14庚酸乙酯（单体）121119107210268239<1-
15庚酸乙酯（二聚体）131714295648<1-
16反式-2-已烯-1-醇（单体）3522332666315485891.2990.002
17反式-2-已烯-1-醇（二聚体）9444613863553871.3300.000
182-乙基吡嗪27343416211294<1-
19萜品油烯1074360169126148<1-
20正辛醛（单体）3492352505224444691.0280.009
21反-4-己烯醛（单体）3602012535764645121.1300.012
22正辛醛（二聚体）12867695154505051.5100.000
23Unknown124241653263553731.3160.000
242-辛酮（二聚体）3631361098188<1-
25乙酸己酯（二聚体）142217392739<1-
26反-4-己烯醛（二聚体）176671065504804831.4760.001
27异戊烯醛（二聚体）271724145133146<1-
28Unknown5502531177145167<1-
29Unknown9201316818173<1-
30乙酸己酯（单体）97143114223139169<1-
31苯甲醛39635111793101<1-
32正己酸乙酯（二聚体）10569449591151133512461.1780.016
33异戊烯醛（单体）14490118307235258<1-
34庚醛（二聚体）8846736601200118712171.6010.022
35δ-3-蒈烯715450790884135111491.5300.049
364-甲基-2-戊醇4292323257496957321.4820.003
37莰烯8714758051384139414471.9450.027
38丙酸乙酯78153013491515214219432.2170.032
39Unknown62031571785324704951.3450.000
40Unknown73452514147887378151.5730.001
41甲乙酮154010539401896132516271.277>0.05
42正己醇（单体）620580443724660677<1-
43乙酸戊酯（二聚体）291334590709527602<1-
44甜瓜醛117101155132112127<1-
45丙酸153124174146164150<1-
46正己醛1302142112401687149416001.1460.024
47庚醛（单体）368349367423345373<1-
48α-松油烯364208316346369394<1-
497，7-二甲基-3-亚甲基双环［2.2.1］庚烷1068703877128511521130<1>0.05
50乙酸戊酯（单体）354329411463316359<1-
51甲酸乙酯5593454268387118231.3550.009
52α-蒎烯（二聚体）343244297445328323<1-
53丁酸乙酯（单聚体）183148185272240262<1-
54α-蒎烯（三聚体）12199132175116103<1-
55丙烯醛1568136412321759175917471.3770.020
56正戊醛113769487212819271058<1-
57Unknown311239241023129611381217<1-
582-戊基呋喃565397601528408461<1-
59Unknown291710951397116713351284<1-
60正丁醇（单体）447401403420338368<1-
61正己酸乙酯（单体）609580570588494525<1-
62冰醋酸（单体）101298194710649891002<1-
63丁醛214316291751205018971861<1-
64Unknown4112210011055120911851212<1-
65正戊醇（二聚体）697681689740728721<1-
664-甲基-2-戊酮144815551347140817271649<1-
672-甲基丁醛186818701567186015821690<1-
68丙醛2888259528153108309231101.320>0.05
69正丁醇（二聚体）720703701726656680<1-
70异丁醛（单体）3416332033493554355835901.0720.003
71乙醇167716701669169417071720<1-
72β-蒎烯（二聚体）331317340308299304<1-
73乙酸乙酯328633213326329033083313<1-
74异丁醛（二聚体）1679194019951111170316651.165>0.05
75Unknown1176916821765178115481679<1-
76Unknown10542525553456530488<1-
77α-蒎烯（单体）446469484547415412<1-
781-戊醇（单体）671631635685583618<1-
79β-蒎烯（单体）11201244955111110371064<1-
80柠檬烯765694699587538521<1-
81乙酸丁酯（单体）205219261289177200<1-
822-辛酮（单体）169355288219162190<1-
83Unknown114243813852281571991.0680.001
842-庚酮1078100710887566166791.4530.001
852-己酮1524888131310999561047<1-
862-戊酮173311091492116192910671.261>0.05
87Unknown89825659356034795551.073>0.05
88冰醋酸（二聚体）1377161516257108117862.0810.001
89乙酸甲酯2893280530709226317773.5130.000
903-甲基丁醇（单体）2823672649562751.1260.002
913-甲基丁醇（二聚体）112287127292931<1-
922-甲基丙酸104150192222823<1-
93乙酸丁酯（二聚体）326440688368258300<1-
94丁酸乙酯（二聚体）441296767281647456<1-
95Unknown13130121327480332359<1-
), ArticleFig(id=1322912491713475057, tenantId=1146029695717560320, journalId=1255847919539208197, articleId=1322912294639903277, language=CN, label=表5, caption=

南北柴胡差异挥发性有机物峰强度信息

, figureFileSmall=null, figureFileBig=null, tableContent=
编号化合物峰强度VIPP值
北柴胡1北柴胡2北柴胡3北柴胡4北柴胡5北柴胡6
1芳樟醇（单体）202033576258<1-
2顺-4-癸烯醛201321605151<1-
3癸醛（单体）2921182702362451.1380.000
4癸醛（二聚体）131414474045<1-
5反-2-辛烯醛（单体）1267986297248259<1-
6反-2-辛烯醛（二聚体）151612394147<1-
7氧化芳樟醇231615152169164<1-
8二甲基三硫醚129102115277238253<1-
92，3-二乙基-5-甲基吡嗪3416162913153111.2780.000
103-辛醇171417544653<1-
11壬醛（单体）115126112223168186<1-
12壬醛（二聚体）151414252023<1-
13正己醇（二聚体）2632501364754794751.1980.023
14庚酸乙酯（单体）121119107210268239<1-
15庚酸乙酯（二聚体）131714295648<1-
16反式-2-已烯-1-醇（单体）3522332666315485891.2990.002
17反式-2-已烯-1-醇（二聚体）9444613863553871.3300.000
182-乙基吡嗪27343416211294<1-
19萜品油烯1074360169126148<1-
20正辛醛（单体）3492352505224444691.0280.009
21反-4-己烯醛（单体）3602012535764645121.1300.012
22正辛醛（二聚体）12867695154505051.5100.000
23Unknown124241653263553731.3160.000
242-辛酮（二聚体）3631361098188<1-
25乙酸己酯（二聚体）142217392739<1-
26反-4-己烯醛（二聚体）176671065504804831.4760.001
27异戊烯醛（二聚体）271724145133146<1-
28Unknown5502531177145167<1-
29Unknown9201316818173<1-
30乙酸己酯（单体）97143114223139169<1-
31苯甲醛39635111793101<1-
32正己酸乙酯（二聚体）10569449591151133512461.1780.016
33异戊烯醛（单体）14490118307235258<1-
34庚醛（二聚体）8846736601200118712171.6010.022
35δ-3-蒈烯715450790884135111491.5300.049
364-甲基-2-戊醇4292323257496957321.4820.003
37莰烯8714758051384139414471.9450.027
38丙酸乙酯78153013491515214219432.2170.032
39Unknown62031571785324704951.3450.000
40Unknown73452514147887378151.5730.001
41甲乙酮154010539401896132516271.277>0.05
42正己醇（单体）620580443724660677<1-
43乙酸戊酯（二聚体）291334590709527602<1-
44甜瓜醛117101155132112127<1-
45丙酸153124174146164150<1-
46正己醛1302142112401687149416001.1460.024
47庚醛（单体）368349367423345373<1-
48α-松油烯364208316346369394<1-
497，7-二甲基-3-亚甲基双环［2.2.1］庚烷1068703877128511521130<1>0.05
50乙酸戊酯（单体）354329411463316359<1-
51甲酸乙酯5593454268387118231.3550.009
52α-蒎烯（二聚体）343244297445328323<1-
53丁酸乙酯（单聚体）183148185272240262<1-
54α-蒎烯（三聚体）12199132175116103<1-
55丙烯醛1568136412321759175917471.3770.020
56正戊醛113769487212819271058<1-
57Unknown311239241023129611381217<1-
582-戊基呋喃565397601528408461<1-
59Unknown291710951397116713351284<1-
60正丁醇（单体）447401403420338368<1-
61正己酸乙酯（单体）609580570588494525<1-
62冰醋酸（单体）101298194710649891002<1-
63丁醛214316291751205018971861<1-
64Unknown4112210011055120911851212<1-
65正戊醇（二聚体）697681689740728721<1-
664-甲基-2-戊酮144815551347140817271649<1-
672-甲基丁醛186818701567186015821690<1-
68丙醛2888259528153108309231101.320>0.05
69正丁醇（二聚体）720703701726656680<1-
70异丁醛（单体）3416332033493554355835901.0720.003
71乙醇167716701669169417071720<1-
72β-蒎烯（二聚体）331317340308299304<1-
73乙酸乙酯328633213326329033083313<1-
74异丁醛（二聚体）1679194019951111170316651.165>0.05
75Unknown1176916821765178115481679<1-
76Unknown10542525553456530488<1-
77α-蒎烯（单体）446469484547415412<1-
781-戊醇（单体）671631635685583618<1-
79β-蒎烯（单体）11201244955111110371064<1-
80柠檬烯765694699587538521<1-
81乙酸丁酯（单体）205219261289177200<1-
822-辛酮（单体）169355288219162190<1-
83Unknown114243813852281571991.0680.001
842-庚酮1078100710887566166791.4530.001
852-己酮1524888131310999561047<1-
862-戊酮173311091492116192910671.261>0.05
87Unknown89825659356034795551.073>0.05
88冰醋酸（二聚体）1377161516257108117862.0810.001
89乙酸甲酯2893280530709226317773.5130.000
903-甲基丁醇（单体）2823672649562751.1260.002
913-甲基丁醇（二聚体）112287127292931<1-
922-甲基丙酸104150192222823<1-
93乙酸丁酯（二聚体）326440688368258300<1-
94丁酸乙酯（二聚体）441296767281647456<1-
95Unknown13130121327480332359<1-
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基于电子鼻和气相离子迁移谱技术分析南北柴胡气味物质差异
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王世丽 1 , 朱娟娟 2, 3 , 吕畅 2, 3 , 戴衍朋 2, 3 , 张军 2, 3 , 石典花 2, 3
中华中医药学刊 | 国家项目点击 2025,43(1): 134-141
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中华中医药学刊 |国家项目点击 2025 , 43 (1) : 134 -141
基于电子鼻和气相离子迁移谱技术分析南北柴胡气味物质差异
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王世丽1, 朱娟娟2, 3, 吕畅2, 3, 戴衍朋2, 3, 张军2, 3 , 石典花2, 3
作者信息
  • 1．山东中医药大学，山东　济南　250014
  • 2．山东省中医药研究院，山东　济南　250014
  • 3．国家中医药管理局中药蜜制和制炭炮制技术与原理重点研究室，山东　济南　250014
通讯作者:
张军（1979-），男，山东济南人，研究员，学士，研究方向：中药炮制。E-mail：。
石典花（1981-），女，山东济南人，研究员，硕士研究生导师，博士，研究方向：中药炮制。E-mail：。
作者简介:

王世丽（1999-），女，山东聊城人，硕士，研究方向：中药炮制。

Analysis of Odor Substance Difference from Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）by Electronic Nose and GC-IMS
Shili WANG1, Juanjuan ZHU2, 3, Chang LYU2, 3, Yanpeng DAI2, 3, Jun ZHANG2, 3 , Dianhua SHI2, 3
Affiliations
  • 1.Shandong University of Traditional Chinese Medicine, Jinan 250014, Shandong, China
  • 2.Shandong Academy of Chinese Medicine, Jinan 250014, Shandong, China
  • 3.Key Unit for Research of Technique and Principle of Honey-processing and Carbonizing of SATCM, Jinan 250014, Shandong, China
出版时间: 2025-01-10 doi: 10.13193/j.issn.1673-7717.2025.01.024
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摘要
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目的

研究南北柴胡气味物质差异。

方法

应用电子鼻技术和气相色谱-离子迁移谱联用（GC-IMS）技术检测南北柴胡挥发性物质差异，采用NIST、IMS数据库对挥发性物质进行定性和定量分析；使用仪器配套的插件对南北柴胡样品进行动态主成分分析（Dynamic PCA），利用SIMCA-P 14.0软件对其进行正交偏最小二乘法-判别分析（OPLS-DA），以微生信平台对其进行聚类热图分析；对比南北柴胡指纹图谱，分析南北柴胡特征物质，筛选Student's t-test P<0.05且正交偏最小二乘法-判别分析模型中变量投影重要性（VIP）>1的挥发性物质为气味差异标志物。

结果

南北柴胡挥发性成分具有显著差异，南柴胡辨识出4个特征物质，分别是癸醛（单体）、氧化芳樟醇、2，3-二乙基-5-甲基吡嗪、异戊烯醛（二聚体）；北柴胡辨识出2个特征物质，分别是3-甲基丁醇（二聚体）、2-甲基丙酸。共筛选出24个气味差异标志物，这些成分可以作为区分南北柴胡的依据。

结论

应用GC-IMS或电子鼻气味辨识技术能够快速鉴别南北柴胡，南柴胡败油气可能与其特征物质异戊烯醛（二聚体）及气味差异标志物癸醛、反-4-己烯醛、正辛醛、庚醛、正己醛、丙烯醛、异丁醛等醛类物质有关。

北柴胡  /  南柴胡  /  电子鼻  /  气相离子迁移谱  /  挥发性物质
Objective

To study the difference in odor substances between Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）.

Methods

Electronic nose technology and gas chromatography-ionmobility spectroscopy（GC-IMS）were used to detectvolatile substances in the Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The NIST and IMS databases were used to qualitatively and quantitatively analyze volatile substances. Plug-ins for the instrumentwas used to perform the dynamic principal component analysis of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The SIMCA-P 14.0 software was used to perform orthogonal partial least squares-discriminant analysis of volatile substances. The microbiotic platform was used to perform cluster heatmap analysis of volatile substances. The fingerprints and the characteristic component of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）sampleswere compared and analyzed. The volatile substances of students't-test with P<0.05 and orthogonal partial least squares-discriminantanalysis with VIP>1 were selected asmarkers of odor differences.

Results

There were significant differences in the volatile components of Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium. Four characteristic substances were identified in Nanchaihu（B. Scorzonerifolium），namely decanal-M，linalool oxide，2，3-diethyl-5-methylpyrazine and 3-methyl-2-butenal-D. Two characteristic substances were identified in Beichaihu（Bupleurum Chinense），namely 3-methylbutanol-D and 2-methylpropanoic acid. A total of 24 markers of odor differences were screened，which could be used as the basis for distinguishing between Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）.

Conclusion

The GC-IMS or electronic nose technology can quickly identify Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）. The gas of rancid oil of Nanchaihu（B. Scorzonerifolium）may be related to its characteristic substance 3-methyl-2-butenal-D and markers of odor differences such as decanal，（E）-2-hexenal，octanal，heptanal，hexanal，acrolein，isobutanal，et al.

Beichaihu（Bupleurum Chinense）  /  Nanchaihu（B. Scorzonerifolium）  /  electronic nose  /  GC-IMS  /  volatile substances
王世丽, 朱娟娟, 吕畅, 戴衍朋, 张军, 石典花. 基于电子鼻和气相离子迁移谱技术分析南北柴胡气味物质差异. 中华中医药学刊, 2025 , 43 (1) : 134 -141 . DOI: 10.13193/j.issn.1673-7717.2025.01.024
Shili WANG, Juanjuan ZHU, Chang LYU, Yanpeng DAI, Jun ZHANG, Dianhua SHI. Analysis of Odor Substance Difference from Beichaihu（Bupleurum Chinense）and Nanchaihu（B. Scorzonerifolium）by Electronic Nose and GC-IMS[J]. Chinese Archives of Traditional Chinese Medicine, 2025 , 43 (1) : 134 -141 . DOI: 10.13193/j.issn.1673-7717.2025.01.024
正文
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柴胡始载于《神农本草经》，被列为上品，具有和解表里，疏肝解郁，升阳举陷，退热截疟之功效。2020版《中华人民共和国药典》中描述柴胡为伞形科植物柴胡Bupleurum chinense DC.或狭叶柴胡Bupleurum scorzonerifolium Willd.的干燥根。按性状不同，分别习称“北柴胡”和“南柴胡”[1]。研究发现南北柴胡中所含有的挥发油、多糖、皂苷类等成分具有一定差异。如南柴胡挥发油含量比北柴胡高2～3倍[2]，孙蓉等[3]对南北柴胡药材中柴胡总皂苷和柴胡皂苷A进行含量测定时，发现北柴胡中柴胡总皂苷及柴胡皂苷A含量均大于南柴胡。南北柴胡的药理药效作用也具有一定差别，如南柴胡的解热作用优于北柴胡，而北柴胡对肝损伤的保护作用优于南柴胡[4]；南柴胡功偏于“升”，能于升散中散热疏肝；北柴胡功偏于“降”，能于疏降中退热泄肝[5]。南北柴胡在外观性状及气味上亦具有一定差异，药典收载为北柴胡气微香，味微苦；南柴胡具败油气[1]。
电子鼻是一种气味分析仪器，能够模拟人类嗅觉系统，具有客观性强、重现性好、不易疲劳的特点[6]，现已广泛应用于中药领域，如不同产地、基原、贮藏时间中药的鉴别及质量控制等[7-10]。气相色谱-离子迁移谱（GC-IMS）是一种新型的气相分离检测技术，结合了气相色谱的高分离能力和离子迁移谱（IMS）的快速检测能力，在食品、工业、中药和环境检测方面有重要应用[11-15]。轩菲洋等[16]采用电子鼻和顶空气质联用技术区分不同产地（山西、内蒙古、黑龙江）柴胡，发现了11种主要差异性物质。王蔚昕[17]发现电子鼻技术能够区分北柴胡与柴胡地方习用品种（小叶黑柴胡、阿尔泰柴胡、三岛柴胡、海拉尔柴胡）。樊洪利等[18]建立了北柴胡与藏柴胡的顶空气相离子迁移谱指纹图谱，应用主成分分析鉴别两种基原柴胡。
南北柴胡的鉴别方法较多，韩丽新[19]依据性状、显微特征及化学成分差异对南北柴胡进行了鉴别。郭泰麟等[20]采用HPLC-ELSD法分别建立南北柴胡的指纹图谱，并进行真伪鉴别。薛英等[21]依据分子标记技术的原理，设计出两对特异性引物用来鉴别南北柴胡，目前尚未发现对南北柴胡气味研究及基于气味特征有效辨识南北柴胡的方法，基于此，本研究应用电子鼻气味辨识和GC-IMS技术探究南北柴胡挥发性气味特征成分及差异成分，建立快速鉴别南北柴胡的方法，为南北柴胡的有效鉴别提供一定的方法和思路。
1　材料
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FlavourSpec®气相色谱-离子迁移谱联用仪（山东海能科学仪器有限公司），MXT-WAX型色谱柱（美国RESTEK公司，30 m×0.53 mm，1 μm），PEN3电子鼻（德国Airsense公司），SQP型电子天平（赛多利斯科学仪器北京有限公司），电热恒温水浴锅（上海精宏实验设备有限公司）。
南北柴胡样品信息见表1，经山东省中医药研究院林慧彬研究员鉴定分别为伞形科植物柴胡Bupleurum Chinense DC.和狭叶柴胡Bupleurum scorzonerifolium Willd.的干燥根。由于目前柴胡品种较为混乱，尤其是市售北柴胡基原混杂，柴胡是济南市十大道地药材之一，本实验所用北柴胡样品为山东百味堂中药饮片有限公司不同种植基地、不同生产批次的北柴胡，能够保障北柴胡基原准确；南柴胡为黑龙江省道地药材，本实验所选南柴胡样品购自黑龙江林甸县大山中草药种植基地和亳州药材市场，产地均为黑龙江，因此本实验是基于道地性和基原准确选择的南北柴胡样品。
2　方法与结果
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2.1　电子鼻检测
2.1.1　样品处理
取2.0 g南北柴胡粉末（过40目筛），精密称定，置于20 mL顶空瓶中加盖密封，于50℃水浴加热10 min后开始检测，每个样品平行测定3次。
2.1.2　进样与测试
采样针插入到顶空样品瓶中，同时插入一个连接活性炭过滤器的针头，位置比采样针深2 cm，以保证样品瓶中的压力平衡[22]。电子鼻检测器由10个金属氧化传感器组成，各传感器检测的物质信息见表2。参数设置：采样间隔1 s，冲洗时间60 s，归零时间5 s，预采样时间5 s，测量时间120 s，腔室流量400 mL/min，初始注射流量400 mL/min。
2.1.3　电子鼻数据处理
由于检测时电子鼻传感器响应值在117～119 s时更稳定，因此取电子鼻检测的10个传感器第117～119 s的响应信号值用仪器自带软件Winmuster进行主成分分析（PCA）、线性判别分析（LDA），并应用SIMCA-P 14.0软件进行正交偏最小二乘法-判别分析（OPLS-DA），分析南北柴胡特征气味的差异，并分析各个传感器对南北柴胡样品区分的贡献度，筛选出对区分南北柴胡贡献度大的传感器，分析这些传感器对应的化合物种类。
2.1.4　电子鼻检测结果分析
电子鼻不同传感器对南北柴胡气味的响应值。应用电子鼻技术辨识南北柴胡样品的气味特征，见插页ⅩⅨ图1（A、B），横坐标为时间，纵坐标为传感器响应值，每条曲线代表一个传感器在120 s内的响应变化。样品采集后，随着挥发性气体在传感器上富集，传感器响应值迅速增大，各个传感器响应值在达到最大值后逐渐下降最终趋于平稳[16]。响应值平稳时（如117 s）南北柴胡各传感器的响应雷达图，见插页ⅩⅨ图1（C、D），从各传感器响应值信号图可以看出南柴胡最高响应值高于北柴胡，且南北柴胡各传感器达到最大值时及平稳时信号值均不同。从各传感器响应值雷达图可以看出南北柴胡的气味差异主要体现在传感器W1S、W2S、W2W 响应值上。
南北柴胡电子鼻检测数据的主成分分析。对南北柴胡的气味特征物质做主成分分析，见插页ⅩⅨ图2。结果显示第一主成分（PC1）的方差贡献率为76.01%，第二主成分（PC2）的方差贡献率为21.15%，PC1和PC2的累计贡献率高达97.16%，说明第一和第二主成分包含了数据的大部分信息。结果表明南北柴胡气味特征具有显著性差异，利用电子鼻气味辨识技术的主成分分析可以有效区分南北柴胡。
南北柴胡电子鼻检测数据的线性判别分析。对南北柴胡的气味特征做线性判别分析，结果见插页ⅩⅩ图3。LDA是一种有监督的数据降维方法，能够缩小组内差异，扩大组间差异。结果显示LD1和LD2方差贡献度分别为96.37%、0.45%，累计方差贡献度为96.82%，能够较好地反映南北柴胡的气味信息。红色点为南柴胡，蓝色点为北柴胡，每个点代表一次检测的样品，结果表明南北柴胡各自聚集，电子鼻气味辨识技术的线性判别分析能够有效区分南北柴胡。
南北柴胡电子鼻检测数据的正交偏最小二乘法-判别分析及差异物质分析。对南北柴胡气味检测数据进行OPLSDA分析，见插页ⅩⅩ图4A。为验证模型的有效性，对该模型进行n＝200的置换检验，见插页ⅩⅩ图4B，结果显示该模型未过拟合。该模型R2Y＝0.972、Q2＝0.81，表明模型的可解释度与预测能力良好。结果显示南柴胡分布于第一、四象限，北柴胡分布于第二、三象限，南北柴胡气味特征具有显著性差异，电子鼻气味辨识技术OPLS-DA能够根据气味差异区分南北柴胡。
根据变量投影重要性（VIP）>1筛选差异贡献度较大的传感器，结果见插页ⅩⅩ图4C。筛选出2种传感器，分别是W1S、W2S，W1S传感器对甲烷等短链烷烃敏感；W2S传感器对醇醚醛酮类灵敏。使用电子鼻仪器自带软件对南北柴胡样品检测结果做Loading分析，见插页ⅩⅩ图4D，结果显示传感器W1S对南北柴胡区分的贡献率最大，其次是W2S，说明南北柴胡气味特征差异主要与短链烷烃、醇醚醛酮类化合物相关[23]。
2.2　气相离子迁移谱检测
2.2.1　样品处理
取1.0 g南北柴胡粉末（过40目筛），精密称定，置20 m L具塞顶空瓶中，80℃孵育15 min后进样，每个样品平行测定3次。
2.2.2　GC-IMS检测条件
系统条件为柱温60℃；载气为N2；离子迁移探测器温度45℃；分析时间30 min。进样体积100 μL；孵育时间15 min；孵育温度80℃；进样针温度85℃；孵化转速500 r/min。E1漂移气体积流量为150 mL/min；E2气相载气体积流量：0～2 min，2 mL/min；2～5 min，2～10 mL/min；5～25 min，10～100 mL/min；25～30 min，100 mL/min。
2.2.3　GC-IMS分析软件
FlavourSpec®气相色谱-离子迁移谱联用仪配套的分析软件包括VOCal和三款插件（Reporter插件、Gallery Plot插件、Dynamic PCA插件），可以分别从不同角度进行样品分析[24]，软件及插件的应用信息见表3。
2.2.4　GC-IMS数据处理
将南北柴胡样品GC-IMS检测数据，应用软件内置的NIST、IMS数据库对物质进行定性和定量分析；利用仪器配套的插件，分析南北柴胡之间的谱图差异，并对比分析南北柴胡挥发性有机物的指纹图谱；对南北柴胡挥发性有机物进行动态主成分分析（Dynamic PCA）、聚类热图分析及正交偏最小二乘法-判别分析；分析南北柴胡特征成分，筛选Student's t-test P<0.05且正交偏最小二乘法-判别分析模型中VIP>1的挥发性物质为气味差异标志物。
2.2.5　南北柴胡GC-IMS检测结果分析
直接对比南北柴胡挥发性有机物差异。使用仪器配套Reporter插件对南北柴胡样品的GC-IMS谱图进行分析，结果见插页ⅩⅪ图5。图为蓝色背景，纵坐标代表气相色谱的保留时间，横坐标代表离子迁移时间。横坐标1.0处红色竖线为RIP峰即反应离子峰，RIP峰两侧的每一个点代表一种挥发性有机物。颜色代表有机物的浓度，白色表示浓度较低，红色表示浓度较高，颜色越深表示浓度越大。结果可以看出，不同柴胡样品中的挥发性有机物存在差异。为了更加明显地对比这种差异，采用差异对比模式：选取其中一个样品的谱图作为参比，其他样品的谱图扣减参比。如果二者挥发性有机物一致，则扣减后的背景为白色，而红色代表该物质的浓度高于参比，蓝色代表该物质的浓度低于参比，结果见插页ⅩⅪ图6。从插页ⅩⅪ图6可以更加明显地看出，南北柴胡样品中的挥发性有机物存在明显差异。
聚类分析。利用Dynamic PCA插件对南北柴胡样品所有峰进行动态主成分分析，结果见插页ⅩⅫ图7。该图可以直观显示不同样品间的差异，样品之间距离近代表差异小，距离远则代表差异明显。由插页ⅩⅫ图7可以看出，南北柴胡各自聚集，区分明显，说明这两种柴胡的区分效果较好，南北柴胡挥发性有机物存在明显差异。
将南北柴胡挥发性有机物峰强度导入微生信（www.bioinformatics.com.cn）绘制其聚类热图，结果见插页ⅩⅫ图8，可以看出挥发性有机物在南北柴胡中的分布规律，图中红色表示高表达，蓝色表示低表达，颜色越深表示表达量越高或越低；橙色组为南柴胡，青色组为北柴胡，可以看出南北柴胡各自聚为一类，且挥发性有机物表达量具有较大差异。
南北柴胡样品中的挥发性有机物指纹图谱对比分析。为明确南北柴胡中具体哪些物质存在差异，利用Gallery Plot插件选取所有峰进行指纹图谱对比，见插页ⅩⅩⅢ图9。图中每一行代表一个样品中选取的全部信号峰，每一列代表同一挥发性有机物在不同样品中的信号峰。其中红框中的物质在南柴胡样品中的含量明显高于北柴胡，黄框中的物质在北柴胡样品中的含量明显高于南柴胡，从图中可以看出南北柴胡样品的完整挥发性有机物信息以及南北柴胡挥发性有机物的差异。
南北柴胡样品中的挥发性有机物定性分析。应用软件内置的VOCal插件和NIST、IMS数据库对南北柴胡中挥发性有机物进行定性分析，所有物质的保留指数和相对迁移时间数据详见表4。
南北柴胡挥发性有机物差异分析　将同一基原3个批次柴胡样品重复测定3次所得峰强度取平均值，分别筛选出南北柴胡中峰强度差异较大的化合物为特征物质，其中峰强度较弱物质规定测定峰强度的平均值<50，且峰强度较强物质规定为两者间峰强度倍数>5。南柴胡共辨识出4种特征物质，包括癸醛（单体）（南250，北23）、氧化芳樟醇（南162，北18）、2，3-二乙基-5-甲基吡嗪（南306，北22）、异戊烯醛（二聚体）（南141，北23）；北柴胡辨识出2种特征物质，分别是3-甲基丁醇（二聚体）（南30，北175）、2-甲基丙酸（南24，北149）。
将同批次柴胡样品重复测定3次所得峰强度取平均值，得到南北柴胡挥发性有机物的峰强度信息，见表5。将其导入SIMCA-P 14.0软件，进行正交偏最小二乘法-判别分析，见插页ⅩⅩⅢ图10A，结果表明南北柴胡挥发性有机物具有显著性差模异。对型进行置换检验Permutation（n＝200），见插页ⅩⅩⅢ图10B，结果显示未过拟合。根据表5应用IBM SPSS Statistics 26对南北柴胡OPLS-DA模型中VIP>1的挥发性有机物进行Student's t-test，筛选VIP>1且P<0.05的挥发性有机物为气味差异标志物，共筛选出24种气味差异标志物，包括7种醛类（癸醛、反-4-己烯醛、正辛醛、庚醛、正己醛、丙烯醛、异丁醛）、4种醇类（正己醇、反式-2-已烯-1-醇、4-甲基-2-戊醇、3-甲基丁醇）、4种酯类（正己酸乙酯、丙酸乙酯、甲酸乙酯、乙酸甲酯）、2种烯类（莰烯、δ-3-蒈烯）、1种酮类（2-庚酮）、1种酸类（乙酸）、1种生物碱类（2，3-二乙基-5-甲基吡嗪）和4种未知化合物。
3　讨论
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本研究应用电子鼻检测技术辨识南北柴胡气味特征物质，通过PCA、LDA和OPLS-DA分析发现3种分析方法均能够依据气味差异区分南北柴胡，并通过分析传感器差异贡献度发现传感器W1S对南北柴胡区分的贡献度最大，其次是W2S，表示南北柴胡中甲烷等短链烷烃、醇、醚、醛、酮类物质差异较大。
利用气相离子迁移谱检测南北柴胡挥发性物质，共辨识出82个挥发性有机物。根据南北柴胡的指纹图谱和峰面积信息，南柴胡共辨识出4个特征物质，分别为癸醛（单体）、氧化芳樟醇、2，3-二乙基-5-甲基吡嗪、异戊烯醛（二聚体）；北柴胡辨识出2个特征物质，分别是3-甲基丁醇（二聚体）、2-甲基丙酸。依据VIP>1且P<0.05筛选出24个气味差异标志物，主要包括醛、醇、酯、烯烃、酮类等化合物，结果表明电子鼻气味辨识和气相离子迁移谱检测结果之间存在较高的相关性，为鉴定南北柴胡提供了理论依据[25]。
通过研究发现南北柴胡气味差异标志物分别为癸醛、反-4-己烯醛、正辛醛、庚醛、正己醛、丙烯醛、异丁醛、正己醇、反式-2-已烯-1-醇、4-甲基-2-戊醇、3-甲基丁醇、正己酸乙酯、丙酸乙酯、甲酸乙酯、乙酸甲酯、莰烯、δ-3-蒈烯、2-庚酮、2，3-二乙基-5-甲基吡嗪、乙酸和4种未知化合物，其中2-庚酮、乙酸、乙酸甲酯、3-甲基丁醇、Unknown11在北柴胡中含量显著高于南柴胡，其余19种化合物在南柴胡中含量均显著高于北柴胡。在实验前期我们应用气相色谱串联质谱方法分析了南北柴胡挥发油成分，发现癸醛、庚醛、正己醛在南柴胡挥发油中的峰面积占比均大于北柴胡，与本实验结果一致。据文献报道酸败油的哈喇味来源于油脂酸败时生成的具有挥发性的低分子醛、酮、脂肪酸、烃、内酯及芳香族化合物，如豆油酸败时会产生醛类物质如戊烯醛、α-庚烯醛、α-己烯醛等[26]。南柴胡具败油气，推测其可能与南柴胡特征物质异戊烯醛（二聚体）及南柴胡含量较高的气味差异标志物癸醛、反-4-己烯醛、正辛醛、庚醛、正己醛、丙烯醛、异丁醛等醛类物质有关。
南北柴胡为药典收载的两种基原，其化学成分、药理药效、外观性状及气味均具有一定差异，本研究首次利用电子鼻气味辨识技术和气相色谱-离子迁移谱联用技术检测南北柴胡中挥发性物质，探究南北柴胡挥发性气味特征成分及差异物质；建立了两种快速鉴别南北柴胡的方法，为提升南北柴胡基原鉴别方法提供参考。
基金
收起
  • 国家中医药管理局第七批全国老中医药专家学术经验继承项目(国中医药人教函〔2022〕76号)
  • 国家中医药管理局中药炮制技术传承基地建设项目(国中医药办规财函〔2022〕185号)
  • 国家中医药管理局全国中药特色技术传承人才培育项目(国中医药人教函〔2022〕96号)
  • 山东省重点研发计划项目(2017GSF19117)
  • 山东省中医药科技发展计划项目(2020M031)
  • 山东省中医药高层次人才培育项目(鲁卫中医药科教字〔2021〕6号)
文献
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2025年第43卷第1期
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doi: 10.13193/j.issn.1673-7717.2025.01.024
  • 首发时间：2026-10-30
  • 出版时间：2025-01-10
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基金
国家中医药管理局第七批全国老中医药专家学术经验继承项目(国中医药人教函〔2022〕76号)
国家中医药管理局中药炮制技术传承基地建设项目(国中医药办规财函〔2022〕185号)
国家中医药管理局全国中药特色技术传承人才培育项目(国中医药人教函〔2022〕96号)
山东省重点研发计划项目(2017GSF19117)
山东省中医药科技发展计划项目(2020M031)
山东省中医药高层次人才培育项目(鲁卫中医药科教字〔2021〕6号)
作者信息
    1．山东中医药大学，山东　济南　250014
    2．山东省中医药研究院，山东　济南　250014
    3．国家中医药管理局中药蜜制和制炭炮制技术与原理重点研究室，山东　济南　250014

通讯作者:

张军（1979-），男，山东济南人，研究员，学士，研究方向：中药炮制。E-mail：。
石典花（1981-），女，山东济南人，研究员，硕士研究生导师，博士，研究方向：中药炮制。E-mail：。
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https://castjournals.cast.org.cn/joweb/zhzyyxk/CN/10.13193/j.issn.1673-7717.2025.01.024
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
Genus		 种数
Number of
species		 占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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